Apparatuses and methods for atomic layer deposition

ABSTRACT

Embodiments of the invention provide apparatuses and methods for atomic layer deposition (ALD), such as plasma-enhanced ALD (PE-ALD). In some embodiments, a PE-ALD chamber is provided which includes a chamber lid assembly coupled with a chamber body having a substrate support therein. In one embodiment, the chamber lid assembly has an inlet manifold assembly containing an annular channel encompassing a centralized channel, wherein the centralized channel extends through the inlet manifold assembly, and the inlet manifold assembly further contains injection holes extending from the annular channel, through a sidewall of the centralized channel, and to the centralized channel. The chamber lid assembly further contains a showerhead assembly disposed below the inlet manifold assembly, a water box disposed between the inlet manifold assembly and the showerhead assembly, and a remote plasma system (RPS) disposed above and coupled with the inlet manifold assembly, and in fluid communication with the centralized channel.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims benefit of U.S. Ser. No. 61/078,321(APPM/012913L), filed Jul. 3, 2008, which is herein incorporated byreference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the invention generally relate to an apparatus and amethod for depositing materials, and more particularly to an atomiclayer deposition chamber configured to deposit a material during aplasma-enhanced process.

2. Description of the Related Art

In the field of semiconductor processing, flat-panel display processingor other electronic device processing, vapor deposition processes haveplayed an important role in depositing materials on substrates. As thegeometries of electronic devices continue to shrink and the density ofdevices continues to increase, the size and aspect ratio of the featuresare becoming more aggressive, e.g., feature sizes of 0.07 μm and aspectratios of 10 or greater. Accordingly, conformal deposition of materialsto form these devices is becoming increasingly important.

While conventional chemical vapor deposition (CVD) has proved successfulfor device geometries and aspect ratios down to 0.15 μm, the moreaggressive device geometries require an alternative depositiontechnique. One technique that is receiving considerable attention isatomic layer deposition (ALD). During an ALD process, reactant gases aresequentially introduced into a deposition chamber containing asubstrate. Generally, a first reactant is pulsed into the depositionchamber and is adsorbed onto the substrate surface. A second reactant ispulsed into the deposition chamber and reacts with the first reactant toform a deposited material. A purge step is typically carried out betweenthe delivery of each reactant gas. The purge step may be a continuouspurge with the carrier gas or a pulse purge between the delivery of thereactant gases. Thermally induced ALD processes are the most common ALDtechnique and use heat to cause the chemical reaction between the tworeactants. While thermal ALD processes work well to deposit somematerials, the processes often have a slow deposition rate. Therefore,fabrication throughput may be impacted to an unacceptable level. Thedeposition rate may be increased at a higher deposition temperature, butmany chemical precursors, especially metal-organic compounds, decomposeat elevated temperatures.

Plasma-enhanced ALD (PE-ALD) may be used to form various materials. Insome examples of PE-ALD processes, a material may be formed from thesame chemical precursors as a thermal ALD process, but at a higherdeposition rate and a lower temperature. Although several variations oftechniques exist, in general, a PE-ALD process provides that a reactantgas and a reactant plasma are sequentially introduced into a depositionchamber containing a substrate. The first reactant gas is pulsed intothe deposition chamber and is adsorbed onto the substrate surface.Thereafter, the reactant plasma is pulsed into the deposition chamberand reacts with the first reactant gas to form a deposited material.Similarly to a thermal ALD process, a purge step may be conductedbetween the delivery of each of the reactants. While PE-ALD processesovercome some of the shortcomings of thermal ALD processes due to thehigh degree of reactivity of the reactant radicals within the plasma,PE-ALD processes have many limitations. PE-ALD process may cause plasmadamage to a substrate (e.g., etching), be incompatible with certainchemical precursors and require additional hardware.

Therefore, there is a need for an apparatus and a process for depositinga material on a substrate by a vapor deposition technique, such as by aPE-ALD process.

SUMMARY OF THE INVENTION

Embodiments of the invention provide an apparatus and a method fordepositing a material on a substrate during atomic layer deposition(ALD) processes, such as a thermal ALD process or a plasma-enhanced ALD(PE-ALD) process. In some embodiments, a deposition chamber for PE-ALDprocesses is provided which includes a substrate support containing asubstrate receiving surface and disposed within a chamber body, achamber lid assembly coupled with the chamber body, and a processingregion disposed between the substrate receiving surface and a lowersurface of a showerhead plate.

In one embodiment, the chamber lid assembly has an inlet manifoldassembly containing an annular channel encompassing a centralizedchannel, wherein the centralized channel extends through the inletmanifold assembly, and the inlet manifold assembly further containsinjection holes extending from the annular channel, through a sidewallof the centralized channel, and to the centralized channel. The chamberlid assembly further contains a showerhead assembly having theshowerhead plate disposed below the inlet manifold assembly, a water boxdisposed between the inlet manifold assembly and the showerheadassembly, and a remote plasma system (RPS) disposed above and coupledwith the inlet manifold assembly, and in fluid communication with thecentralized channel.

The inlet manifold assembly may contain or be made from aluminum or analuminum alloy. In some examples, the inlet manifold assembly containsan aluminum alloy, such as an aluminum alloy containing magnesium andsilicon.

In some embodiments, the injection holes have a first plurality ofinjection holes extending towards or substantially towards a centralaxis of the centralized channel. The injection holes may also have asecond plurality of injection holes that usually extend at a differentangle than the first plurality of holes. In some examples, the secondplurality of injection holes extend tangential or substantiallytangential towards the sidewall of the centralized channel. The secondplurality of injection holes may be disposed along the sidewall of thecentralized channel and between the first plurality of injection holesand the showerhead assembly. Generally, the second plurality ofinjection holes may extend away from or substantially away from thecentralized channel. In one example, the first plurality of injectionholes contains three or more injection holes. In another example, thesecond plurality of injection holes contains three or more injectionholes. Each injection hole may have a diameter within a range from about0.06 inches to about 0.12 inches.

Embodiments provide that the chamber may further contain a gas manifoldassembly coupled with and in fluid communication with the inlet manifoldassembly. The gas manifold assembly may have a first conduit coupledwith and in fluid communication with the annular channel. A valveassembly may be coupled with and in fluid communication with the firstconduit. In one example, the valve assembly may contain a mass flowcontroller (MFC) to enable an ALD deposition process. The gas manifoldassembly may also have a second conduit coupled with and in fluidcommunication with the annular channel. Alternatively, the gas manifoldassembly may have a second conduit coupled with and in fluidcommunication with the RPS. The RPS is usually disposed at the upper endof the centralized channel while the showerhead assembly is disposed atthe lower end of the centralized channel.

In another embodiment, a method for depositing a material on a substrateis provided which includes exposing the substrate sequentially to atitanium precursor gas and a nitrogen plasma to form a titanium nitridematerial on the substrate during an ALD process within a depositionchamber. In some examples, the titanium precursor gas containstetrakis(dimethylamido)titanium and the nitrogen plasma is generatedfrom a RPS. The deposition chamber contains a chamber lid assemblycoupled with a chamber body. The chamber lid assembly has an inletmanifold assembly containing an annular channel encompassing acentralized channel. The centralized channel extends through the inletmanifold assembly.

In one embodiment, the ALD process includes flowing the titaniumprecursor gas into the annular channel within the inlet manifoldassembly, flowing the titanium precursor gas from the annular channelinto the centralized channel via a plurality of injection holes whichextend from the annular channel through a sidewall of the centralizedchannel, and to the centralized channel, flowing the titanium precursorgas through the centralized channel, through a showerhead assemblyattached with the chamber lid assembly, and absorbing a layer of thetetrakis(dimethylamido)titanium on the substrate. The method of the ALDprocess further provides generating the nitrogen plasma by igniting aprocess gas containing nitrogen (N₂) with the RPS, flowing the nitrogenplasma through the centralized channel, through the showerhead assembly,and towards the substrate, and exposing the layer of thetetrakis(dimethylamido)titanium to the nitrogen plasma to form thetitanium nitride material on the substrate.

In some embodiments, the method provides flowing the titanium precursorgas from a first plurality of injection holes towards or substantiallytowards a central axis of the centralized channel. In other embodiments,the method provides flowing the titanium precursor gas from a secondplurality of injection holes extending tangential or substantiallytangential towards the sidewall of the centralized channel.Alternatively, the method provides flowing the titanium precursor gasthrough the second plurality of injection holes to form a circular gasflow of the titanium precursor gas through the centralized channel. Inseveral embodiments, the circular flow pattern of the titanium precursorgas or the nitrogen plasma may be a flow pattern such as a vortex flowpattern, a helix flow pattern, a spiral flow pattern, a swirl flowpattern, a twirl flow pattern, a twist flow pattern, a coil flowpattern, a corkscrew flow pattern, a curl flow pattern, a whirlpool flowpattern, or a derivative thereof. In some examples, the first pluralityof injection holes contains three or more injection holes and/or thesecond plurality of injection holes contains three or more injectionholes.

In another embodiment, a showerhead assembly for a vapor depositionprocess is provided which includes a showerhead plate having a topsurface, a bottom surface, and a radius extending from the center to theouter edge of the showerhead plate, a first plurality of holes in fluidcommunication with the top surface and the bottom surface, positionedwithin a first zone extending from the center of the showerhead plate toabout 25% of the radius of the showerhead plate, and each hole has adiameter of less than 0.1 inches, and a second plurality of holes influid communication with the top surface and the bottom surface,positioned within a second zone extending from about 25% of the radiusof the showerhead plate to about the outer edge of the showerhead plate,and each hole has a diameter of greater than 0.1 inches.

In some examples, the diameter of the first plurality of holes may beabout 0.09 inches or less. The diameter of the second plurality of holesmay be about 0.11 inches or greater, such as about 0.12 inches orgreater, such as about 0.13 inches or greater. In other examples, theshowerhead plate may have an increasing hole density radially extendingtowards the outer edge. The showerhead plate may contain or be made fromaluminum, aluminum alloys, aluminum-plated metals, stainless steel,nickel, nickel alloys, nickel-plated aluminum, nickel-plated metal,chromium, iron, alloys thereof, derivatives thereof, or combinationsthereof. In some examples, the showerhead plate contains an aluminumalloy, such as an aluminum alloy containing magnesium and silicon.

In other embodiments, the showerhead plate contains a lower hole densityat the center of the showerhead plate and a higher hole density at theedge of the showerhead plate. These lower/higher hole densities help todirect more nitrogen plasma or nitrogen radicals to edge of theshowerhead plate for better uniformity as gas inlet was located in thecenter position. In addition, gradual change of hole sizes from small tolarge at center to edge of showerhead plate. In another aspect, theshowerhead plate may contain holes with a diameter within a range fromabout 0.08 inches to about 0.13 inches. This hole size reduces therecombination of nitrogen radicals, which improves the film properties.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the features of the invention are attainedand can be understood in detail, a more particular description of theinvention, briefly summarized above, may be had by reference to theembodiments thereof which are illustrated in the appended drawings.

It is to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 depicts an inlet manifold assembly as described in embodimentsherein;

FIGS. 2A-2C depict an upper inlet manifold as described in embodimentsherein;

FIGS. 3A-3D depict a lower inlet manifold as described in embodimentsherein;

FIGS. 4A-4B depict schematic views of a portion of the lower inletmanifold as described in embodiments herein;

FIG. 5A depicts an alternative inlet manifold assembly as described inanother embodiment herein;

FIG. 5B depicts another alternative inlet manifold assembly as describedin another embodiment herein;

FIGS. 6A-6D depict schematic views of a showerhead assembly as describedin embodiments herein;

FIG. 7A depicts a schematic view of the showerhead assembly with onetype of showerhead plate as described in an embodiments herein;

FIGS. 7B-7E depict schematic views of various other showerhead plates asdescribed in embodiments herein;

FIGS. 8A-8C depict schematic views of a water box as described inembodiments herein; p FIGS. 9A-9D depict schematic views of a pumpingring as described in embodiments herein;

FIGS. 10A-10B depict schematic views of a pumping ring assembly asdescribed in some embodiments herein;

FIG. 11A depicts a schematic and partial view of a chamber body assemblyas described in embodiments herein;

FIG. 11B depicts a schematic and partial view of an alternative chamberbody assembly as described in other embodiments herein;

FIGS. 12A-12B depict schematic views of a chamber lid plate as describedin some embodiments herein;

FIGS. 13A-13E depict schematic views of a gas manifold assembly asdescribed in embodiments herein;

FIG. 14 depicts a schematic view of a chamber lid assembly as describedin some embodiments herein;

FIG. 15 depicts a schematic view of another chamber lid assembly asdescribed in other embodiments herein;

FIGS. 16A-16B depict schematic views of a chamber lid assembly asdescribed in embodiments herein;

FIG. 17 depicts a schematic view of an ALD chamber assembly as describedin embodiments herein;

FIGS. 18A-18B depict schematic views of a gas purge assembly asdescribed in embodiments herein; and

FIG. 19 depicts a schematic view of a processing system containing avariety of deposition chambers including ALD chambers, as described inembodiments herein.

DETAILED DESCRIPTION Deposition Chamber

Embodiments of the invention provide an apparatus configured to formmaterials during atomic layer deposition (ALD) processes, such as athermal ALD process or a plasma-enhanced ALD (PE-ALD) process. Otherembodiments of the invention provide ALD and PE-ALD processes forforming various materials, such as titanium nitride. In someembodiments, a processing system or chamber is configured to expose asubstrate to a sequence of gases and plasmas during a PE-ALD process. Inone embodiment, a deposition chamber is configured to perform a PE-ALDprocess using a remote plasma system (RPS) for igniting the plasma. Inanother embodiment, the deposition chamber is configured to perform athermal ALD process.

FIG. 1 depicts inlet manifold assembly 100 which may be utilized withinor by thermal or plasma-enhanced ALD systems, chambers, and processes,such as described herein. Inlet manifold assembly 100 contains upperinlet manifold 110 and lower inlet manifold 130. Upper inlet manifold110 and lower inlet manifold 130 may each independently contain or beformed from a metal such as aluminum, aluminum alloys, aluminum-platedmetals, steel, stainless steel, nickel, nickel alloys (such as INCONEL®or HASTELLOY®), nickel-plated aluminum, nickel-plated metal, chromium,iron, alloys thereof, derivatives thereof, or combinations thereof. Inone embodiment, both upper inlet manifold 110 and lower inlet manifold130 contain or are formed from aluminum or an aluminum alloy, forexample, an aluminum alloy containing magnesium and silicon, such asaluminum 6061.

The aluminum alloy may contain silicon, magnesium, iron, copper, andother elements, such as manganese, chromium, zinc, or titanium. In someembodiments, the aluminum alloy may have a concentration by weight ofaluminum within a range from about 95% to about 99%, magnesium within arange from about 0.8% to about 1.2%, silicon within a range from about0.4% to about 0.8%, copper within a range from about 0.15% to about0.40%, and iron within a range from about 0.2% to about 0.70%. In oneexample, an aluminum alloy may have the following composition by weight:Mg (1.00% less), Si (0.60%), Cu (0.30%), Fe (0.7% or less), Mn (0.15%),Cr (0.20%), Zn (0.25% or less), Ti (0.15% or less), and Al (balance). Inanother example, the aluminum alloy may be aluminum 6061.

Upper inlet manifold 110 is further illustrated in FIGS. 2A-2C and lowerinlet manifold 130 is further illustrated in FIGS. 3A-3D. Upper inletmanifold 110 may be disposed on top of and partially over lower inletmanifold 130. Lower surfaces 112 and 114 of upper inlet manifold 110 maybe respectively disposed on upper surfaces 132 and 134 of lower inletmanifold 130. Upper surface 132 contains groove 133 and upper surface134 contains groove 135. Grooves 133 and 135 may each contain an o-ring,which is used to form a seal between lower surface 112 and upper surface132, as well, between lower surface 114 and upper surface 134. Annularchannel 140 is formed between upper inlet manifold 110 and lower inletmanifold 130. Annular channel 140 encircles or encompasses centralizedchannel 150, which is formed through upper inlet manifold 110 and lowerinlet manifold 130.

Centralized channel 150 contains channel 125 within upper inlet manifold110 and channel 145 within lower inlet manifold 130. Centralized channel150 may have an inner diameter which stays fairly consistent alongcentral axis 152. In one embodiment, the inner diameter of centralizedchannel 150 for a chamber adapted to process a 300 mm diameter substrateis within a range from about 0.2 inches to about 2 inches, preferably,from about 1 inch to about 1.8 inches, and more preferably, from about1.2 inches to about 1.5 inches, for example, about 1.4 inches.

Upper inlet manifold 110 contains inlet 120 and outlet 121, which arealigned with central axis 152 and in fluid communication withcentralized channel 150. A remote plasma system (RPS) may be fluidlycoupled to inlet 120. Upper inlet manifold 110 contains inlet 122extending from outside sidewall 115 of upper inlet manifold 110, throughupper inlet manifold 110, and into annular channel 140. In one example,upper inlet manifold 110 may also contain tapered surface 111 at outlet121.

In one embodiment, lower inlet manifold 130 contains injection holes 136and injection holes 138. Both sets of injection holes 136 and 138 extendthrough sidewall 139 of lower inlet manifold 130 and provide fluidcommunication between annular channel 140 and centralized channel 150.FIGS. 4A-4B provide a schematic view of a portion of lower inletmanifold 130 depicting injection holes 136 and 138, as described by oneembodiment herein. In some embodiments, injection holes 136 may bepositioned directly towards or substantially towards central axis 152extending through the middle of centralized channel 150, as depicted inFIG. 4A. Injection holes 138 are positioned tangentially towards orsubstantially tangentially towards sidewall 151 of centralized channel150, as depicted in FIG. 4B.

Throughout the embodiments, there is at least one injection hole 136 andat least one injection hole 138. As depicted in FIGS. 4A-4B, lower inletmanifold 130 contains three holes for injection holes 136 and threeholes for injection holes 138. In other embodiments, lower inletmanifold 130 may contain 1, 2, 3, 4, 5, 6, or more injections holes 136and independently contain 1, 2, 3, 4, 5, 6, or more injections holes138. Injection holes 136 and 138 may independently have a diameterwithin a range from about 0.02 inches to about 0.5 inches, preferably,from about 0.04 inches to about 0.4 inches, preferably, from about 0.05inches to about 0.2 inches, and more preferably, from about 0.06 inchesto about 0.12 inches, and more preferably, from about 0.07 inches toabout 0.11 inches. In one example, injection holes 136 have a diameterof about 0.089 inches and injection holes 138 have a diameter of about0.100 inches

Injection holes 138 may be positioned tangentially towards orsubstantially tangentially towards sidewall 151 of centralized channel150. A gas flow coming from each of injection holes 138 combines withincentralized channel 150 to form a gas flow having a circular direction.Injection holes 136 may be positioned directly towards or substantiallytowards central axis 152. A gas flow coming from each of injection holes136 combines within centralized channel 150 at or near central axis 152.The combined gas flow forms a downward gas flow extending downcentralized channel 150 towards the formed by injection holes 138. Thedownward gas flow from injection holes 136 and the circular gas flowfrom injection holes 138 combine to form a sweeping vortex gas flow thatextends down centralized channel 150, along and past rounded corner 131of lower inlet manifold 130, towards the showerhead. Although the exactgeometry of sweeping vortex gas flow through centralized channel 150 isnot known, it is believed that the process gas or plasma may travel witha circular gas flow having a flow pattern of a vortex flow pattern, ahelix flow pattern, a spiral flow pattern, a swirl flow pattern, a twirlflow pattern, a twist flow pattern, a coil flow pattern, a corkscrewflow pattern, a curl flow pattern, a whirlpool flow pattern, orderivatives thereof.

In several alternative embodiments, FIG. 5A depicts inlet manifoldassembly 500 a and FIG. 5B depicts inlet manifold assembly 500 b whichmay be utilized within or by thermal or plasma-enhanced ALD systems,chambers, and processes, such as described herein. Inlet manifoldassemblies 500 a and 500 b contain upper inlet manifold 510 and lowerinlet manifold 530. Upper inlet manifold 510 may be disposed on top ofand partially within lower inlet manifold 530. Lower surface 512 ofupper inlet manifold 510 may be disposed on upper surface 532 of lowerinlet manifold 530. Upper surface 532 contains groove 533. Groove 533may contain an o-ring, which is used to form a seal between lowersurface 512 and upper surface 532. Also, for inlet manifold assembly 500a, side surface 514 of upper inlet manifold 510 may be disposed againstside surface 534 of lower inlet manifold 530. Side surface 534 containsgroove 535. Groove 535 may contain an o-ring, which is used to form aseal between side surface 514 and side surface 534.

Annular channel 540 is formed between upper inlet manifold 510 and lowerinlet manifold 530. Annular channel 540 encircles or encompassescentralized channel 550, which is formed through upper inlet manifold510 and lower inlet manifold 530. Centralized channel 550 contains upperchannel 525 within upper inlet manifold 510 and lower channel 545 withinlower inlet manifold 530.

In another embodiment, upper inlet manifold 510 contains injection holes536 and injection holes 538. Both sets of injection holes 536 and 538extend through sidewall 539 of upper inlet manifold 510 and providefluid communication between annular channel 540 and centralized channel550. FIG. 5A provides a schematic view of a portion of lower inletmanifold 530 depicting injection holes 536 and 538, as described by oneembodiment herein. In some embodiments, injection holes 536 arepositioned directly towards or substantially towards a central axisextending through the middle of centralized channel 550. Injection holes538 are positioned tangentially towards or substantially tangentiallytowards sidewall 551 of centralized channel 550.

Centralized channel 550 contains channel 525 within upper inlet manifold510 and channel 545 within lower inlet manifold 530. Centralized channel550 may have an inner diameter which stays fairly consistent alongcentral axis 552. In one embodiment, the inner diameter of centralizedchannel 550 for a chamber adapted to process a 300 mm diameter substrateis within a range from about 0.2 inches to about 2 inches, preferably,from about 1 inch to about 1.8 inches, and more preferably, from about1.2 inches to about 1.5 inches, for example, about 1.4 inches.

Upper inlet manifold 510 contains inlet 520 and outlet 521, which arealigned with central axis 552 and in fluid communication withcentralized channel 550. A remote plasma system (RPS) may be fluidlycoupled to inlet 520. Upper inlet manifold 510 contains inlet 522extending from outside sidewall 515 of upper inlet manifold 510, throughupper inlet manifold 510, and into annular channel 540. In one example,upper inlet manifold 510 may also contain tapered surface 511 at outlet521.

Upper inlet manifold 510 contains inlet 520, which may be aligned withcentral axis 552 and in fluid communication with centralized channel550. A remote plasma system (RPS) may be fluidly coupled to inlet 520.Upper inlet manifold 510 contains inlet 522 extending from outsidesidewall 515 of upper inlet manifold 510, through upper inlet manifold510, and into annular channel 540. In one example, upper inlet manifold510 may also contain tapered surface 511.

Upper inlet manifold 510 and lower inlet manifold 530 may eachindependently contain or be formed from a metal such as aluminum,aluminum alloys, aluminum-plated metals, steel, stainless steel, nickel,nickel alloys (such as INCONEL® or HASTELLOY®), nickel-plated aluminum,nickel-plated metal, chromium, iron, alloys thereof, derivativesthereof, or combinations thereof. In one example, both upper inletmanifold 510 and lower inlet manifold 530 independently contain or areformed from aluminum or an aluminum alloy. In some examples, thealuminum alloy contains magnesium and silicon, such as aluminum 6061.

Throughout the embodiments, there is at least one injection hole 536 andat least one injection hole 538. Lower inlet manifold 530 contains 3injection holes 536 and 3 injection holes 538. In other embodiments,lower inlet manifold 530 may contain 1, 2, 3, 4, 5, 6, or moreinjections holes 536 and independently contain 1, 2, 3, 4, 5, 6, or moreinjections holes 538. Injection holes 536 and 538 may independently havea diameter within a range from about 0.02 inches to about 0.5 inches,preferably, from about 0.04 inches to about 0.4 inches, preferably, fromabout 0.05 inches to about 0.2 inches, and more preferably, from about0.06 inches to about 0.12 inches, and more preferably, from about 0.07inches to about 0.11 inches. In one example, injection holes 536 have adiameter of about 0.089 inches and injection holes 538 have a diameterof about 0.100 inches

Injection holes 538 may be positioned tangentially towards orsubstantially tangentially towards sidewall 551 of centralized channel550. A gas flow coming from each of injection holes 538 combines withincentralized channel 550 to form a gas flow having a circular direction.Injection holes 536 may be positioned directly towards or substantiallytowards central axis 552. A gas flow coming from each of injection holes536 combines within centralized channel 550 at or near central axis 552.The combined gas flow forms a downward gas flow extending downcentralized channel 550 towards the circular gas flow formed byinjection holes 538. The downward gas flow from injection holes 536 andthe circular gas flow from injection holes 538 combine to form asweeping vortex gas flow that extends down centralized channel 550,along and past rounded corner 531 of lower inlet manifold 530, towardsthe showerhead. Although the exact geometry of sweeping vortex gas flowthrough centralized channel 550 is not known, it is believed that theprocess gas may travel in a circular flow pattern, a vortex flowpattern, a helix flow pattern, a spiral flow pattern, a swirl flowpattern, a twirl flow pattern, a twist flow pattern, a coil flowpattern, a corkscrew flow pattern, a curl flow pattern, a whirlpool flowpattern, or derivatives thereof.

FIGS. 6A-6D and 7A depict showerhead assembly 600 containing showerheadplate 602 having holes 620. FIGS. 7B-7E depict showerhead plate 602which may be utilized in showerhead assembly 600. Holes 620 extendthrough showerhead plate 602, from upper surface 610 to lower surface612 of showerhead plate 602. In one embodiment, showerhead assembly 600contains showerhead plate 602 disposed on inner ring 604, which isdisposed on outer ring 606. Showerhead plate 602, inner ring 604, andouter ring 606 may be a single piece or separate isolatable pieces orparts which together form showerhead assembly 600. For example,showerhead plate 602, inner ring 604, and outer ring 606 may be onepiece, two pieces, or multiple pieces which together form showerheadassembly 600. In some embodiments, showerhead assembly 600, showerheadplate 602, inner ring 604, and/or outer ring 606 may independently eachcontain or be formed from a metal such as aluminum, aluminum alloys,aluminum-plated metals, steel, stainless steel, nickel, nickel alloys(such as INCONEL® or HASTELLOY®), nickel-plated aluminum, nickel-platedmetal, chromium, iron, alloys thereof, derivatives thereof, orcombinations thereof. In one example, showerhead assembly 600 and/orshowerhead plate 602 independently contains or is formed from aluminumor an aluminum alloy. In some examples, the aluminum alloy containsmagnesium and silicon, such as aluminum 6061.

In an alternative embodiment, showerhead assembly 600 and/or showerheadplate 602 may contain or be formed from a material such as quartz,ceramic, fused quartz, sapphire, pyrolytic boron nitrite (PBN) material,glass, silicate materials, silica materials, alumina materials, zirconiamaterials, alloys thereof, derivatives thereof, and combinationsthereof. In one example, showerhead assembly 600 and/or showerhead plate602 contains or is formed from quartz. In one embodiment, upper surface610 and lower surface 612 may be roughened (e.g., machined) to have amean roughness (Ra) of at least about 300 microinch or greater.

In one embodiment, showerhead assembly 600 has an increasing holedensity radially extending towards the outer edge. Upper surface 610 ofshowerhead plate 602 receives a process gas or plasma for distributinginto a process region through holes 620. Holes 620 pass throughshowerhead plate 602 from upper surface 610 to lower surface 612 andprovide fluid communication therethrough. Holes 620 may have a varietyof sizes and be contained across upper surface 610 and lower surface 612in multiple patterns. Each hole of the plurality of holes 620 may have adiameter within a range from about 0.05 inches to about 0.16 inches,preferably, from about 0.07 inches to about 0.14 inches, and morepreferably, from about 0.08 inches to about 0.13 inches. In oneembodiment, showerhead plate 602 has at least about 300 holes, such asfrom about 320 holes to about 500 holes. In one example, showerheadplate 602 contains about 350 holes.

In another embodiment, showerhead assembly 600 or showerhead plate 602may have multiple rings of holes 620 and may have holes 620 of varyingdiameters, as depicted in FIGS. 7A-7E. Showerhead assembly 600 orshowerhead plate 602 may have 15 rings of holes 620 (FIGS. 7A-7D) orless rings, such as 8 rings (FIG. 7E). FIG. 7B depicts Rings A-Oextending radially towards the outer edge of showerhead plate 602. Thediameter of holes 620 may increase, as well as the overall hole densityof showerhead plate 602, extending radially towards the outer edge ofshowerhead plate 602.

In some embodiments, showerhead assembly 600 or showerhead plate 602contains a first plurality of holes 620 in fluid communication uppersurface 610 and lower surface 612. The first plurality of holes 620 arepositioned within a first zone extending from the center of showerheadplate 602 to about 25% of the radius of showerhead plate 602, and eachhole has a diameter of less than 0.1 inches. Showerhead assembly 600contains a second plurality of holes in fluid communication with uppersurface 610 and lower surface 612. The second plurality of holes 620 arepositioned within a second zone extending from about 25% of the radiusof showerhead plate 602 to about the outer edge of showerhead assembly600, and each hole has a diameter of greater than 0.1 inches. In someexamples the diameter of the first plurality of holes is about 0.09inches or less. In other examples, the diameter of the second pluralityof holes is about 0.11 inches or greater, preferably, about 0.12 inchesor greater, and more preferably, about 0.13 inches or greater.

FIGS. 8A-8C depict water box 800 used to regulate the temperature byremoving heat from deposition chambers lid assemblies, such as chamberlid assembly 1400 or 1500. Water box 800 may be positioned on top ofshowerhead assembly 600. Water box 800 contains a centralizedpassageway, such as opening 820, through body 802. Inner upper surface803 and outer upper surface of body 802 both encircle opening 820. Lowersurface 806 of water box 800 faces showerhead assembly 600 withinchamber lid assembly 1400. Opening 820 is adapted to receive inletmanifold assembly 100, which may be positioned on ledge surface 814.Water box 800 may contain or be formed from a metal such as aluminum,aluminum alloys (e.g., aluminum magnesium silicon alloys, such asaluminum 6061), aluminum-plated metals, stainless steel, nickel, nickelalloys (such as INCONEL® or HASTELLOY®), nickel-plated aluminum,nickel-plated metal, chromium, iron, alloys thereof, derivativesthereof, or combinations thereof. In one example, water box 800 maycontain or is formed from aluminum or an aluminum alloy.

Water box 800 removes heat from chamber lid assembly 1400 or 1500, suchas from showerhead assembly 600. Inner upper surface 803 of water box800 contains inlet 810 and outlet 812 that are in fluid communicationwith passageway 830. During a deposition process, a fluid at an initialtemperature is administered into water box 800 through inlet 810. Thefluid absorbs heat while traveling along passageway 830. The fluid at ahigher temperature is removed from water box 800 through outlet 812.

The fluid may be in liquid, gas or supercritical state and is capable ofadsorbing and dissipating heat in a timely manner. Liquids that may beused in water box 800 include water, oil, alcohols, glycols, glycolethers, other organic solvents, supercritical fluids (e.g., CO₂)derivatives thereof or mixtures thereof. Gases may include nitrogen,argon, air, hydrofluorocarbons (HFCs), or combinations thereof.Preferably, water box 800 is supplied with water or a water/alcoholmixture.

Inlet nozzle 811 may be coupled with and in fluid communication withinlet 810 and outlet nozzle 813 may be coupled with and in fluidcommunication with outlet 812, as depicted in FIG. 14. Inlet 810 may beadapted to receive inlet nozzle 811 connected to a line (e.g., hose) influid communication with a fluid source. Similarly, outlet 812 may beadapted to receive outlet nozzle 813 connected to a line in fluidcommunication with a fluid return. The fluid source and fluid return maybe an in-house cooling system or an independent cooling system. Thefluid lines may be a tube, a hose, or a conduit.

In one embodiment, the fluid may be administered into water box 800 at atemperature within a range from about −20° C. to about 40° C.,preferably, from about 0° C. to about 20° C. The temperature, flow rate,and fluid composition may be adjusted accordingly to remove theappropriate amount of heat from chamber lid assembly 1400 includingshowerhead assembly 600 while maintaining water box 800 at apredetermined temperature. Water box 800 may be maintained at apredetermined temperature within a range from about 0° C. to about 100°C., preferably, from about 18° C. to about 65° C., and more preferably,from about 20° C. to about 50° C. In an alternative embodiment,passageway 830 may have a variety of different geometries that may beused to maintain the predetermined temperature. Passageway 830 mayinclude a partial loop, a single loop, multiple loops, or containbranches or spurs there around.

FIGS. 9A-9D depict pumping ring 900 used in embodiments herein. Pumpingring 900 contains upper ring 902, middle ring 904, and lower ring 906.Upper surface 912 of pumping ring 900 is the outer surface of upper ring902 and lower surface 914 of pumping ring 900 is the outer surface oflower ring 906. Pumping ring 900 contains a centralized passageway, suchas opening 920, extending therethrough and encompassed by sidewall 908.Upper ring 902, middle ring 904, and lower ring 906 encircle opening920. Pumping ring 900 also contains opening 922 disposed between middlering 904 and lower ring 906.

Pumping ring 900 contains a plurality of holes 910 between upper ring902 and middle ring 904. Holes 910 provide fluid communication fromopening 920 and through sidewall 908 and pumping ring 900. Pumping ring900 may contain from about 50 holes to about 100 holes, such as about 72holes. Holes 910 may have a diameter within a range from about 0.1inches to about 0.5 inches, preferably, from about 0.25 inches to about0.40 inches. Pumping ring 900 may contain or be formed from a metal suchas aluminum, aluminum alloys (e.g., aluminum magnesium silicon alloys,such as aluminum 6061), aluminum-plated metals, stainless steel, nickel,nickel alloys (such as INCONEL® or HASTELLOY®), nickel-plated aluminum,nickel-plated metal, chromium, iron, alloys thereof, derivativesthereof, or combinations thereof.

FIGS. 10A-10B and FIG. 11B depict pumping ring assembly 940 containingouter shield ring 950 encompassing pumping ring 900, as described insome embodiments herein. Channel 952 is formed within pumping ringassembly 940, between pumping ring 900 and outer shield ring 950, and isin fluid communication with opening 920 via holes 910. Outer shield ring950 may contain or be formed from a metal such as aluminum, aluminumalloys (e.g., aluminum magnesium silicon alloys, such as aluminum 6061),aluminum-plated metals, stainless steel, nickel, nickel alloys (such asINCONEL® or HASTELLOY®), nickel-plated aluminum, nickel-plated metal,chromium, iron, alloys thereof, derivatives thereof, or combinationsthereof.

FIG. 11A depicts chamber body assembly 1100 and FIG. 11B depicts chamberbody assembly 1150, which both may be contained within chamber lidassemblies 1400 and 1500, as described in embodiments herein. FIG. 11Adepicts chamber body 990 within chamber body assembly 1100, as describedin one embodiment herein. Chamber body assembly 1100 contains edge ring980 encompassing or encircling substrate support 960. Substrate support960 contains heater 962, which may be used to heat substrate support960, substrates disposed thereon, and surrounding processing region. Inanother embodiment, chamber body assembly 1150 also contains pumpingring assembly 940, which includes outer shield 950 encompassing orencircling pumping ring 900, depicted in FIG. 11B.

FIG. 12A-12B depicts chamber lid plate 1000, as described in someembodiments herein. Upper surface 1004 of chamber lid plate 1000 isillustrated in FIG. 12A while lower surface 1006 of chamber lid plate1000 is illustrated in FIG. 12B. Showerhead assembly 600, or othershower heads, may be disposed within opening 1020 of chamber lid plate1000, as depicted in FIGS. 14-16A. Chamber lid plate 1000 may contain orbe formed from a metal such as aluminum, aluminum alloys (e.g., aluminummagnesium silicon alloys, such as aluminum 6061), aluminum-platedmetals, stainless steel, nickel, nickel alloys (such as INCONEL® orHASTELLOY®), nickel-plated aluminum, nickel-plated metal, chromium,iron, alloys thereof, derivatives thereof, or combinations thereof.

FIGS. 13A-13E depict gas manifold assembly 1300, that may be containedwithin chamber lid assemblies 1400 and 1500, as described in embodimentsherein. Gas manifold assembly 1300 contains at least one gas conduit,but usually contains two, three, or more gas conduits. FIGS. 13A-13Edepict gas conduits 1302 and 1304 extending throughout manifold housing1308 of gas manifold assembly 1300. Gas conduit 1302 extends from inlet1310, through manifold housing 1308, and to outlet 1312 at outlet plate1314. Gas conduit 1304 extends from inlet 1320, through manifold housing1308, and to outlet 1322 at outlet plate 1314. Inlet 1310 may be coupledwith and in fluid communication with a first precursor source containinga first chemical precursor while inlet 1320 may be coupled with and influid communication with a second precursor source containing a secondchemical precursor.

In one embodiment, FIGS. 14 and 16A schematically depicts chamber lidassembly 1400 containing remote plasma system (RPS) 1405 positioned oninlet manifold assembly 100 and in fluid communication with centralizedchannel 150. Lower inlet manifold 130 of centralized channel 150contains injection holes 136 and injection holes 138, which extendthrough sidewall 139 of lower inlet manifold 130 and provide fluidcommunication between annular channel 140 and centralized channel 150.In some embodiments, injection holes 136 may be positioned directlytowards or substantially towards central axis 152 extending through themiddle of centralized channel 150. Injection holes 138 may be positionedtangentially towards or substantially tangentially towards sidewall 151of centralized channel 150. FIG. 16B illustrates lid assembly cover 1406over chamber lid assembly 1400.

In another embodiment, FIG. 15 schematically depicts lid assembly 1500containing RPS 1405 positioned on inlet manifold assembly 500 b and influid communication with centralized channel 550. Upper inlet manifold510 of centralized channel 550 contains injection holes 536 andinjection holes 538, which provide fluid communication between annularchannel 540 and centralized channel 550. In some embodiments, injectionholes 536 may be positioned directly towards or substantially towardscentral axis 552 extending through the middle of centralized channel550. Injection holes 538 may be positioned tangentially towards orsubstantially tangentially towards sidewall 551 of centralized channel550.

A plasma system and a chamber body assembly that may be used incombination with chamber lid assemblies 1400 and 1500 is the TXZ® CVD,chamber available from Applied Materials, Inc., located in Santa Clara,Calif. Further disclosure of plasma systems, ALD chambers, anddeposition chambers is described in commonly assigned U.S. Pat. Nos.5,846,332, 6,079,356, and 6,106,625, which are incorporated herein byreference in their entirety, to provide further disclosure for a plasmagenerator, a plasma chamber, an ALD chamber body, a substrate support orpedestal, and chamber liners.

In another embodiment, FIG. 17 illustrates ALD chamber assembly 1700containing chamber lid assembly 1400 equipped with RPS 1405. FIGS.18A-18B illustrate gas purge assembly 1800 that may be used with ALDchamber assembly 1700 containing chamber lid assembly 1400. Gas purgeassembly 1800 contains vacuum pumping system 1810 containing a pluralityof valve assemblies 1830.

Gas sources (not shown) provide precursor gas, carrier gas, or purge gasto chamber lid assembly 1400 or 1500 and/or with ALD chamber assembly1700 through a conduit system. In one embodiment, gas sources may becoupled with and in fluid communication with gas manifold assembly 1300.Gas sources may be directly or indirectly connected to a chemical supplyor a gas supply. The chemical or gas supplies include a tank, anampoule, a bubbler, a vaporizer or another container used to store,transfer, or form a chemical precursor. The chemical or gas supply mayalso be from an in-house source. Proper control and regulation of thegas flows from gas sources to gas manifold assembly 1300 are performedby valve assemblies 1720 and 1722 coupled to control unit 1750, as wellas valve assembly 1730. Gas manifold assembly 1300 introduces processgases into ALD chamber assembly 1700 and may optionally be heated toprevent condensation of any gases within the conduits or lines of gasmanifold assembly 1300.

Each valve assembly 1720 and 1722 may have a diaphragm and a valve seat.The diaphragm may be biased open or closed and may be actuated closed oropen respectively. The diaphragms may be pneumatically actuated or maybe electrically actuated. Examples of pneumatically actuated valves areavailable from Fujikin and Veriflow and examples of electricallyactuated valves are available from Fujikin. Control unit 1750 may becoupled to valve assemblies 1720 and 1722 to control actuation of thediaphragms of the valves. Pneumatically actuated valves may providepulses of gases in time periods as low as about 0.020 seconds.Electrically actuated valves may provide pulses of gases in time periodsas low as about 0.005 seconds. Generally pneumatically and electricallyactuated valves may provide pulses of gases in time periods as high asabout 3 seconds. Although higher time period for gas pulsing ispossible, a typical ALD process utilizes ALD valves to generate pulsesof gas while being opened for an interval of about 5 seconds or less,preferably about 3 seconds or less, and more preferably about 2 secondsor less. In one embodiment, an ALD valve pulses for an interval within arange from about 0.005 seconds to about 3 seconds, preferably from about0.02 seconds to about 2 seconds and more preferably from about 0.05seconds to about 1 second. An electrically actuated valve typicallyrequires the use of a driver coupled between the valve and control unit1750. In another embodiment, each valve assembly 1720 and 1722 maycontain a mass flow controller (MFC) to control gas dispersion, gas flowrates, and other attributes to an ALD pulse sequence.

A precursor or a gas delivery system within an ALD apparatus is used tostore and dispense chemical precursors, carrier gases, purge gases orcombinations thereof. The delivery system may contain valves (e.g., ALDvalves or MFCs), conduits, reservoirs, ampoules and bubblers, heaterand/or control unit systems, which may be used with gas manifoldassembly 1300, chamber lid assembly 1400 or 1500, ALD chamber assembly1700, and/or processing system 1900. In one example, a delivery systemmay contain gas sources and valve assemblies 1720 and 1722 coupled tocontrol unit 1750. Delivery systems configured for an ALD process systemare described in commonly assigned U.S. Ser. No. 11/127,753, filed May12, 2005, and published as US 2005-0271812, U.S. Ser. No. 11/119,388,filed Apr. 29, 2005, published as US 2005-0252449, and now abandoned,U.S. Ser. No. 10/281,079, filed Oct. 25, 2002 and published as US2003-0121608, and U.S. Ser. No. 10/700,328, filed Nov. 3, 2003,published as US 2005-009859, and now abandoned, which are incorporatedherein by reference in their entirety.

Control unit 1750, such as a programmed personal computer, work stationcomputer, or the like, may be coupled to ALD chamber assembly 1700 tocontrol processing conditions. For example, control unit 1750 may beconfigured to control flow of various process gases and purge gases fromgas sources through valve assemblies 1720 and 1722 during differentstages of a substrate process sequence. Illustratively, control unit1750 comprises central processing unit (CPU), support circuitry, andmemory containing associated control software.

Software routines, as required, may be stored in the memory or executedby a remotely located source (e.g., computer or server). The softwareroutines are executed to initiate process recipes or sequences. Thesoftware routines, when executed, transform the general purpose computerinto a specific process computer that controls the chamber operationduring a chamber process. For example, software routines may be used toprecisely control the activation of gas sources through valve assemblies1720 and 1722 during the execution of process sequences according to theembodiments described herein. Alternatively, the software routines maybe performed in the hardware, as an application specific integratedcircuit or other type of hardware implementation or a combination ofsoftware or hardware.

Control unit 1750 may be one of any form of general purpose computerprocessor that can be used in an industrial setting for controllingvarious chambers and sub-processors. The CPU may use any suitablememory, such as random access memory, read only memory, floppy diskdrive, compact disc drive, hard disk, or any other form of digitalstorage, local or remote. Various support circuits may be coupled to theCPU for supporting ALD chamber assembly 1700. Control unit 1750 may becoupled to another controller that is located adjacent individualchamber components, such as programmable logic controllers of valveassemblies 1720 and 1722. Bi-directional communications between controlunit 1750 and various other components of ALD chamber assembly 1700 arehandled through numerous signal cables collectively referred to assignal buses. In addition to control of process gases and purge gasesfrom gas sources, valve assemblies 1720 and 1722 and any programmablelogic controllers, control unit 1750 may be configured to be responsiblefor automated control of other activities used during a fabricationprocess. Control unit 1750 may be connected with and configured tocontrol the plasma generator controller for RPS 1405, vacuum pumpingsystem 1810, and a support controller, including temperature monitoringand control of lift pins (not shown).

FIG. 19 depicts processing system 1900 containing various depositionchambers for depositing and removing materials onto substrates. In oneexample, processing system 1900 contains two deposition chambers 1940and 1942, such as ALD chambers configured to form titanium nitride, asdescribed herein. In some embodiments, load locks 1912 a and 1912 b maybe positioned on interface 1914. Processing system 1900 containstransfer robots 1910 a, 1910 b positioned on platform 1902. Depositionchambers 1916 a, 1916 b, 1920, 1922, 1924, 1926, 1930, 1940, and 1942may be disposed around the perimeter of and coupled with platform 1902.

In several examples, deposition chambers 1916 a and 1916 b may eachindependently be a heating chamber or an annealing chamber, depositionchambers 1920 and 1922 may each independently be a degassing chamber, avacuum chamber, or an annealing chamber, and deposition chambers 1924and 1926 may each independently be a preclean chamber, a plasma chamber,a sublimation chamber, or an annealing chamber (e.g., a SICONI® precleanchamber). Deposition chambers 1930, 1940, and/or 1942 may eachindependently be a deposition chamber, such as a CVD, an ALD, or a PVDchamber. In one example, deposition chamber 1930 may be an ESIP® Tichamber and be utilized to deposit a titanium containing material (e.g.,metallic titanium, titanium nitride, or other titanium alloys). Inanother example, deposition chambers 1940 and 1942 may eachindependently be may be an TXZ® ALD-TiN chamber and be utilized todeposit a titanium containing material (e.g., metallic titanium,titanium nitride, or other titanium alloys) during an ALD process.

Titanium Nitride PE-ALD Process

Embodiments of the invention provide methods for depositing a variety ofmaterial (e.g., titanium nitride) on a substrate by a vapor depositionprocess, such as atomic layer deposition (ALD) or plasma-enhanced ALD(PE-ALD). In one aspect, the process has little or no initiation delayand maintains a fast deposition rate while forming a titanium material,such as metallic titanium, titanium nitride, titanium silicon nitride,or derivatives thereof.

In one embodiment, titanium precursors that may be used with the PE-ALDprocesses described herein include tetrakis(dimethylamino)titanium(TDMAT), tetrakis(diethylamino)titanium (TDEAT), titanium tetrachloride(TiCl₄), and derivatives thereof. The PE-ALD processes described hereininclude sequentially exposing a substrate with a nitrogen precursor anda nitrogen plasma or other ionized reagent plasma.

In one example, a process gas containing TDMAT is pulsed into inlet 122,through annular channel 140, from injection holes 136 and 138, and intocentralized channel 150 and nitrogen plasma is sequentially pulsed froma RPS into centralized channel 150 from inlet 120. Both the process gascontaining TDMAT and the nitrogen plasma are sequentially pulsed to andthrough showerhead assembly 600. Thereafter, the substrate issequentially exposed to the process gas and the nitrogen plasma.

In one embodiment, a titanium nitride material may be formed during aPE-ALD process containing a constant flow of a reagent gas whileproviding sequential pulses of a titanium precursor and a plasma. Inanother embodiment, a titanium material may be formed during anotherPE-ALD process that provides sequential pulses of a titanium precursor(e.g., TDMAT) and a reagent plasma (e.g., nitrogen plasma). In both ofthese embodiments, the reagent is generally ionized during the process.The PE-ALD process provides that the plasma is generated external fromthe deposition chamber, such as by a remote plasma generator (RPS)system. During PE-ALD processes, a plasma may be generated from amicrowave (MW) frequency generator or a radio frequency (RF) generator.In another embodiment, a titanium material may be formed during athermal ALD process that provides sequential pulses of a titaniumprecursor and a reagent.

Chamber lid assemblies 1400 or 1500 may be utilized during ALD processesdescribed in embodiments herein and may be coupled with various ALDchamber bodies described herein. Other ALD chambers may also be usedduring some of the embodiments described herein and are available fromApplied Materials, Inc., located in Santa Clara, Calif. A detaileddescription of an ALD chamber may be found in commonly assigned U.S.Pat. Nos. 6,916,398 and 6,878,206, and commonly assigned U.S. Ser. No.10/281,079, filed on Oct. 25, 2002, and published as US 2003-0121608,which are hereby incorporated by reference in their entirety. In anotherembodiment, a chamber configured to operate in both an ALD mode as wellas a conventional CVD mode may be used to deposit titanium materials isdescribed in commonly assigned U.S. Pat. No. 7,204,886, which isincorporated herein by reference in its entirety.

In some embodiment, the deposition chamber may be pressurized at apressure within a range from about 0.01 Torr to about 80 Torr,preferably from about 0.1 Torr to about 10 Torr, and more preferably,from about 0.5 Torr to about 2 Torr during several of the ALD processesdescribed herein. Also, the chamber or the substrate may be heated to atemperature of less than about 500° C., preferably, about 400° C. orless, such as within a range from about 200° C. to about 400° C., andmore preferably, from about 340° C. to about 370° C., for example, about360° C. during several of the ALD processes described herein. DuringPE-ALD processes, a plasma may be ignited by an external source, such asa remote plasma generator or a remote plasma system (RPS). A plasma maybe generated by a microwave (MW) generator or a radio frequency (RF)generator. For example, the plasma generator may be set to have a poweroutput within a range from about 1 kilowatts (kW) to about 40 kW,preferably, from about 2 kW to about 20 kW, and more preferably, fromabout 4 kW to about 10 kW.

The substrate may be for example, a silicon substrate having aninterconnect pattern defined in one or more dielectric material layersformed thereon. In example, the substrate contains an adhesion layerthereon, while in another example, the substrate contains a dielectricsurface. The deposition chamber conditions such as, the temperature andpressure, are adjusted to enhance the adsorption of the process gases onthe substrate so as to facilitate the reaction of the titanium precursorand the reagent gas.

In one embodiment, the substrate may be exposed to a reagent gasthroughout the whole ALD cycle. The substrate may be exposed to atitanium precursor gas formed by passing a carrier gas (e.g., nitrogenor argon) through an ampoule of a titanium precursor. The ampoule may beheated depending on the titanium precursor used during the process. Inone example, an ampoule containing TDMAT may be heated to a temperaturewithin a range from about 25° C. to about 80° C. The titanium precursorgas usually has a flow rate within a range from about 100 sccm to about2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm, andmore preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The titanium precursor gas and the reagent gas may becombined to form a deposition gas. A reagent gas usually has a flow ratewithin a range from about 100 sccm to about 3,000 sccm, preferably, fromabout 200 sccm to about 2,000 sccm, and more preferably, from about 500sccm to about 1,500 sccm. In one example, nitrogen plasma is used as areagent gas with a flow rate of about 1,500 sccm. The substrate may beexposed to the titanium precursor gas or the deposition gas containingthe titanium precursor and the reagent gas for a time period within arange from about 0.1 seconds to about 8 seconds, preferably, from about1 second to about 5 seconds, and more preferably, from about 2 secondsto about 4 seconds. The flow of the titanium precursor gas may bestopped once a layer of the titanium precursor is adsorbed on thesubstrate. The layer of the titanium precursor may be a discontinuouslayer, a continuous layer, or even multiple layers.

The substrate and chamber may be exposed to a purge step after stoppingthe flow of the titanium precursor gas. The flow rate of the reagent gasmay be maintained or adjusted from the previous step during the purgestep. Preferably, the flow of the reagent gas is maintained from theprevious step. Optionally, a purge gas may be administered into thedeposition chamber with a flow rate within a range from about 100 sccmto about 2,000 sccm, preferably, from about 200 sccm to about 1,000sccm, and more preferably, from about 300 sccm to about 700 sccm, forexample, about 500 sccm. The purge step removes any excess titaniumprecursor and other contaminants within the deposition chamber. Thepurge step may be conducted for a time period within a range from about0.1 seconds to about 8 seconds, preferably, from about 1 second to about5 seconds, and more preferably, from about 2 seconds to about 4 seconds.The carrier gas, the purge gas and the process gas may contain nitrogen,hydrogen, ammonia, argon, neon, helium or combinations thereof. In apreferred embodiment, the carrier gas contains nitrogen.

Thereafter, the flow of the reagent gas may be maintained or adjustedbefore igniting a plasma. The substrate may be exposed to the plasma fora time period within a range from about 0.1 seconds to about 20 seconds,preferably, from about 1 second to about 10 seconds, and morepreferably, from about 2 seconds to about 8 seconds. Thereafter, theplasma power was turned off. In one example, the reagent may be ammonia,nitrogen, hydrogen or a combination thereof to form an ammonia plasma, anitrogen plasma, a hydrogen plasma, or a combined plasma. The reactantplasma reacts with the adsorbed titanium precursor on the substrate toform a titanium material thereon. In one example, the reactant plasma isused as a reducing agent to form metallic titanium. However, a varietyof reactants may be used to form titanium materials having a wide rangeof compositions. In one example, a boron-containing reducing compound(e.g., diborane) is used to form a titanium material containing boride.In another example, a silicon-containing reducing compound (e.g.,silane) is used to form a titanium material containing silicide.

The deposition chamber was exposed to a second purge step to removeexcess precursors or contaminants from the previous step. The flow rateof the reagent gas may be maintained or adjusted from the previous stepduring the purge step. An optional purge gas may be administered intothe deposition chamber with a flow rate within a range from about 100sccm to about 2,000 sccm, preferably, from about 200 sccm to about 1,000sccm, and more preferably, from about 300 sccm to about 700 sccm, forexample, about 500 sccm. The second purge step may be conducted for atime period within a range from about 0.1 seconds to about 8 seconds,preferably, from about 1 second to about 5 seconds, and more preferably,from about 2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of thetitanium material is deposited on the substrate. The titanium materialmay be deposited with a thickness less than 1,000 Å, preferably lessthan 500 Å and more preferably from about 10 Å to about 100 Å, forexample, about 30 Å. The processes as described herein may deposit atitanium material at a rate of at least 0.15 Å/cycle, preferably, atleast 0.25 Å/cycle, more preferably, at least 0.35 Å/cycle or faster. Inanother embodiment, the processes as described herein overcomeshortcomings of the prior art relative as related to nucleation delay.There is no detectable nucleation delay during many, if not most, of theexperiments to deposit the titanium materials.

In another embodiment, a titanium material may be formed during anotherPE-ALD process that provides sequentially exposing the substrate topulses of a titanium precursor and an active reagent, such as a reagentplasma. The substrate may be exposed to a titanium precursor gas formedby passing a carrier gas through an ampoule containing a titaniumprecursor, as described herein. The titanium precursor gas usually has aflow rate within a range from about 100 sccm to about 2,000 sccm,preferably, from about 200 sccm to about 1,000 sccm, and morepreferably, from about 300 sccm to about 700 sccm, for example, about500 sccm. The substrate may be exposed to the deposition gas containingthe titanium precursor and the reagent gas for a time period within arange from about 0.1 seconds to about 8 seconds, preferably, from about1 second to about 5 seconds, and more preferably from about 2 seconds toabout 4 seconds. The flow of the titanium precursor gas may be stoppedonce the titanium precursor is adsorbed on the substrate. The titaniumprecursor may be a discontinuous layer, continuous layer or evenmultiple layers.

Subsequently, the substrate and chamber are exposed to a purge step. Apurge gas may be administered into the deposition chamber during thepurge step. In one aspect, the purge gas is the reagent gas, such asammonia, nitrogen or hydrogen. In another aspect, the purge gas may be adifferent gas than the reagent gas. For example, the reagent gas may beammonia and the purge gas may be nitrogen, hydrogen or argon. The purgegas may have a flow rate within a range from about 100 sccm to about2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm, andmore preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The purge step removes any excess titanium precursor andother contaminants within the deposition chamber. The purge step may beconducted for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably, from about 2 seconds to about 4 seconds. A carrier gas,a purge gas and a process gas may contain nitrogen, hydrogen, ammonia,argon, neon, helium, or mixtures thereof.

The substrate and the adsorbed titanium precursor thereon may be exposedto the reagent gas during the next step of the ALD process. Optionally,a carrier gas may be administered at the same time as the reagent gasinto the deposition chamber. The reagent gas may be ignited to form aplasma. The reagent gas usually has a flow rate within a range fromabout 100 sccm to about 3,000 sccm, preferably, from about 200 sccm toabout 2,000 sccm, and more preferably, from about 500 sccm to about1,500 sccm. In one example, ammonia is used as a reagent gas with a flowrate of about 1,500 sccm. The substrate may be exposed to the plasma fora time period within a range from about 0.1 seconds to about 20 seconds,preferably, from about 1 second to about 10 seconds, and morepreferably, from about 2 seconds to about 8 seconds. Thereafter, theplasma power may be turned off. In one example, the reagent may beammonia, nitrogen, hydrogen or combinations thereof, while the plasmamay be an ammonia plasma, a nitrogen plasma, a hydrogen plasma or acombination thereof. The reactant plasma reacts with the adsorbedtitanium precursor on the substrate to form a titanium material thereon.Preferably, the reactant plasma is used as a reducing agent to formmetallic titanium. However, a variety of reactants may be used to formtitanium materials having a wide range of compositions, as describedherein.

The deposition chamber may be exposed to a second purge step to removeexcess precursors or contaminants from the deposition chamber. The flowof the reagent gas may have been stopped at the end of the previous stepand started during the purge step, if the reagent gas is used as a purgegas. Alternative, a purge gas that is different than the reagent gas maybe administered into the deposition chamber. The reagent gas or purgegas may have a flow rate within a range from about 100 sccm to about2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm, andmore preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The second purge step may be conducted for a time periodwithin a range from about 0.1 seconds to about 8 seconds, preferably,from about 1 second to about 5 seconds, and more preferably, from about2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of thetitanium material is deposited on the substrate. The titanium materialmay be deposited with a thickness less than 1,000 Å, preferably lessthan 500 Å and more preferably from about 10 Å to about 100 Å, forexample, about 30 Å. The processes as described herein may deposit atitanium material at a rate of at least 0.15 Å/cycle, preferably, atleast 0.25 Å/cycle, more preferably, at least 0.35 Å/cycle or faster. Inanother embodiment, the processes as described herein overcomeshortcomings of the prior art relative as related to nucleation delay.There is no detectable nucleation delay during many, if not most, of theexperiments to deposit the titanium materials.

The titanium precursor and the reagent may be sequentially introducedinto the deposition chamber during a thermal ALD process or a PE-ALDprocess. The titanium materials formed by process herein includemetallic titanium, titanium nitride, titanium silicon nitride, orderivatives thereof. A suitable reagent for forming a titanium materialmay be a nitrogen precursor or a reducing gas and include nitrogen(e.g., N₂ or atomic-N), hydrogen (e.g., H₂ or atomic-H), ammonia (NH₃),hydrazine (N₂H₄), silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈),tetrasilane (Si₄H₁₀). dimethylsilane (SiC₂H₈), methyl silane (SiCH₆),ethylsilane (SiC₂H₈), chlorosilane (ClSiH₃), dichlorosilane (Cl₂SiH₂),hexachlorodisilane (Si₂Cl₆), borane (BH₃), diborane (B₂H₆),triethylborane (Et₃B), derivatives thereof, plasmas thereof, orcombinations thereof.

The time interval for the pulse of the titanium precursor is variabledepending upon a number of factors such as, for example, the volumecapacity of the deposition chamber employed, the vacuum system coupledthereto and the volatility/reactivity of the reactants used during theALD process. For example, (1) a large-volume deposition chamber may leadto a longer time to stabilize the process conditions such as, forexample, carrier/purge gas flow and temperature, requiring a longerpulse time; (2) a lower flow rate for the process gas may also lead to alonger time to stabilize the process conditions requiring a longer pulsetime; and (3) a lower chamber pressure means that the process gas isevacuated from the deposition chamber more quickly requiring a longerpulse time. In general, the process conditions are advantageouslyselected so that a pulse of the titanium precursor provides a sufficientamount of precursor so that at least a monolayer of the titaniumprecursor is adsorbed on the substrate. Thereafter, excess titaniumprecursor remaining in the chamber may be removed from the depositionchamber by the constant carrier gas stream in combination with thevacuum system.

The time interval for each of the pulses of the titanium precursor andthe reagent gas may have the same duration. That is, the duration of thepulse of the titanium precursor may be identical to the duration of thepulse of the reagent gas. For such an embodiment, a time interval (T₁)for the pulse of the titanium precursor (e.g., TDMAT) is equal to a timeinterval (T₂) for the pulse of the reagent gas (e.g., nitrogen plasma).

Alternatively, the time interval for each of the pulses of the titaniumprecursor and the reagent gas may have different durations. That is, theduration of the pulse of the titanium precursor may be shorter or longerthan the duration of the pulse of the reagent gas. For such anembodiment, a time interval (T₁) for the pulse of the titanium precursoris different than the time interval (T₂) for the pulse of the reagentgas.

In addition, the periods of non-pulsing between each of the pulses ofthe titanium precursor and the reagent gas may have the same duration.That is, the duration of the period of non-pulsing between each pulse ofthe titanium precursor and each pulse of the reagent gas is identical.For such an embodiment, a time interval (T₃) of non-pulsing between thepulse of the titanium precursor and the pulse of the reagent gas isequal to a time interval (T₄) of non-pulsing between the pulse of thereagent gas and the pulse of the titanium precursor. During the timeperiods of non-pulsing only the constant carrier gas stream is providedto the deposition chamber.

Alternatively, the periods of non-pulsing between each of the pulses ofthe titanium precursor and the reagent gas may have different duration.That is, the duration of the period of non-pulsing between each pulse ofthe titanium precursor and each pulse of the reagent gas may be shorteror longer than the duration of the period of non-pulsing between eachpulse of the reagent gas and the titanium precursor. For such anembodiment, a time interval (T₃) of non-pulsing between the pulse of thetitanium precursor and the pulse of the reagent gas is different from atime interval (T₄) of non-pulsing between the pulse of the reagent gasand the pulse of titanium precursor. During the time periods ofnon-pulsing only the constant carrier gas stream is provided to thedeposition chamber.

Additionally, the time intervals for each pulse of the titaniumprecursor, the reagent gas and the periods of non-pulsing therebetweenfor each deposition cycle may have the same duration. For such anembodiment, a time interval (T₁) for the titanium precursor, a timeinterval (T₂) for the reagent gas, a time interval (T₃) of non-pulsingbetween the pulse of the titanium precursor and the pulse of the reagentgas and a time interval (T₄) of non-pulsing between the pulse of thereagent gas and the pulse of the titanium precursor each have the samevalue for each deposition cycle. For example, in a first depositioncycle (C₁), a time interval (T₁) for the pulse of the titanium precursorhas the same duration as the time interval (T₁) for the pulse of thetitanium precursor in subsequent deposition cycles (C₂. . . C_(n)).Similarly, the duration of each pulse of the reagent gas and the periodsof non-pulsing between the pulse of the titanium precursor and thereagent gas in the first deposition cycle (C₁) is the same as theduration of each pulse of the reagent gas and the periods of non-pulsingbetween the pulse of the titanium precursor and the reagent gas insubsequent deposition cycles (C₂ . . . C_(n)), respectively.

Alternatively, the time intervals for at least one pulse of the titaniumprecursor, the reagent gas and the periods of non-pulsing therebetweenfor one or more of the deposition cycles of the titanium materialdeposition process may have different durations. For such an embodiment,one or more of the time intervals (T₁) for the pulses of the titaniumprecursor, the time intervals (T₂) for the pulses of the reagent gas,the time intervals (T₃) of non-pulsing between the pulse of the titaniumprecursor and the reagent gas and the time intervals (T₄) of non-pulsingbetween the pulses of the reagent gas and the titanium precursor mayhave different values for one or more deposition cycles of the cyclicaldeposition process. For example, in a first deposition cycle (C₁), thetime interval (T₁) for the pulse of the titanium precursor may be longeror shorter than one or more time interval (T₁) for the pulse of thetitanium precursor in subsequent deposition cycles (C₂. . . C_(n)).Similarly, the durations of the pulses of the reagent gas and theperiods of non-pulsing between the pulse of the titanium precursor andthe reagent gas in the first deposition cycle (C₁) may be the same ordifferent than the duration of each pulse of the reagent gas and theperiods of non-pulsing between the pulse of the titanium precursor andthe reagent gas in subsequent deposition cycles (C₂ . . . C_(n)).

In some embodiments, a constant flow of a carrier gas or a purge gas maybe provided to the deposition chamber modulated by alternating periodsof pulsing and non-pulsing where the periods of pulsing alternatebetween the titanium precursor and the reagent gas along with thecarrier/purge gas stream, while the periods of non-pulsing include onlythe carrier/purge gas stream.

A PE-ALD chamber, as described herein, may be used to form manymaterials including tantalum, tantalum nitride, titanium, titaniumnitride, ruthenium, tungsten, tungsten nitride, ruthenium, cobalt,hafnium, silicides thereof, oxides thereof, derivatives thereof, orcombinations thereof, as well as other materials.

In one example, a copper seed layer may be formed on the titaniumnitride material by a CVD process and thereafter, bulk copper isdeposited to fill the interconnect by an ECP process. In anotherexample, a copper seed layer may be formed on the titanium nitridematerial by a PVD process and thereafter, bulk copper is deposited tofill the interconnect by an ECP process. In another example, a copperseed layer may be formed on the titanium nitride material by anelectroless process and thereafter, bulk copper is deposited to fill theinterconnect by an ECP process. In another example, the titanium nitridematerial serves as a seed layer to which a copper bulk fill is directlydeposited by an ECP process or an electroless deposition process.

In another example, a tungsten seed layer may be formed on the titaniumnitride material by a PE-ALD process and thereafter, bulk tungsten isdeposited to fill the interconnect by a CVD process or a pulsed-CVDprocess. In another example, a tungsten seed layer may be formed on thetitanium nitride material by a PVD process and thereafter, bulk tungstenis deposited to fill the interconnect by a CVD process or a pulsed-CVDprocess. In another example, a tungsten seed layer may be formed on thetitanium nitride material by a PE-ALD process and thereafter, bulktungsten is deposited to fill the interconnect by an ECP process. Inanother example, the titanium nitride material serves as a seed layer towhich a tungsten bulk fill is directly deposited by a CVD process or apulsed-CVD process.

Several integration sequence are conducted in order to form a titaniumnitride material within an interconnect. In one example, the subsequentsteps follow: a) pre-clean of the substrate; b) deposition of a barrierlayer (e.g., ALD of TiN); c) deposition of titanium nitride by PE-ALD;and d) deposition of seed copper by electroless, ECP or PVD followed bydeposition of bulk copper by ECP. In another example, the subsequentsteps follow: a) deposition of a barrier layer (e.g., PE-ALD of TiN); b)punch through step; c) deposition of titanium nitride by PE-ALD; and d)deposition of seed copper by electroless, ECP or PVD followed bydeposition of bulk copper by ECP. In another example, the subsequentsteps follow: a) deposition of titanium nitride by PE-ALD; b) punchthrough step; c) deposition of titanium nitride by PE-ALD; and d)deposition of seed copper by electroless, ECP or PVD followed bydeposition of bulk copper by electroless, ECP or PVD. In anotherexample, the subsequent steps follow: a) deposition of titanium nitrideby PE-ALD; b) punch through step; c) deposition of titanium nitride byPE-ALD; and d) deposition of copper by electroless or ECP. In anotherembodiment, the subsequent steps follow: a) pre-clean of the substrate;b) deposition of titanium nitride by PE-ALD; and c) deposition of seedcopper by electroless, ECP or PVD followed by deposition of bulk copperby ECP. In another example, the subsequent steps follow: a) depositionof a barrier layer (e.g., PE-ALD of TiN); b) deposition of titaniumnitride by PE-ALD; c) punch through step; d) deposition of titaniumnitride by PE-ALD; and e) deposition of seed copper by electroless, ECPor PVD followed by deposition of bulk copper by ECP. In another example,the subsequent steps follow: a) deposition of a barrier layer (e.g.,PE-ALD of TiN); b) punch through step; c) deposition of a barrier layer(e.g., PE-ALD of TiN); d) deposition of titanium nitride by PE-ALD; andd) deposition of seed copper by electroless, ECP or PVD; and e)deposition of bulk copper by ECP. In one example, the subsequent stepsfollow: a) pre-clean of the substrate; b) deposition of a barrier layer(e.g., PE-ALD of TiN); c) deposition of titanium nitride by PE-ALD; andd) deposition of copper bulk by electroless or ECP.

In some embodiments, titanium nitride materials formed by the PE-ALDprocesses described herein, have very little or no chlorineconcentration or impurity. In one example, the titanium precursor gascontains TDMAT and the nitrogen plasma is formed from nitrogen (N₂). Thesubstrate may be heated to a temperature within a range from about 340°C. to about 370° C. The plasma may be applied at a power within a rangefrom about 4 kW to about 10 kW. The nitrogen gas may have a flow ratewithin a range from about 200 sccm to about 2,000 sccm. The internalpressure of the deposition chamber may be within a range from about 500mTorr to about 2 Torr.

The pre-clean steps include methods to clean or purify the via, such asthe removal of residue at the bottom of the via (e.g., carbon) orreduction of copper oxide to copper metal. Punch through steps include amethod to remove material (e.g., barrier layer) from the bottom of thevia to expose conductive layer, such as copper. Further disclosure ofpunch through steps is described in more detail in the commonlyassigned, U.S. Pat. No. 6,498,091, which is incorporated herein in itsentirety by reference. The punch through steps may be conducted within adeposition chamber, such as either a barrier chamber or a clean chamber.In embodiments of the invention, clean steps and punch through steps areapplied to titanium nitride barrier layers. Further disclosure ofoverall integrated methods are described in more detail in the commonlyassigned, U.S. Pat. No. 7,049,226, which is incorporated herein in itsentirety by reference.

The titanium nitride materials formed during the PE-ALD processes asdescribed herein generally have a sheet resistance of less than 2,000μΩ-cm, preferably, less than 1,000 μΩ-cm, and more preferably, less than500 μΩ-cm.

A “substrate surface,” as used herein, refers to any substrate ormaterial surface formed on a substrate upon which film processing isperformed during a fabrication process. For example, a substrate surfaceon which processing can be performed include materials such as silicon,silicon oxide, strained silicon, silicon on insulator (SOI), carbondoped silicon oxides, silicon nitride, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Barrier layers, metals or metal nitrides on a substratesurface include titanium, titanium nitride, tungsten nitride, tantalum,tantalum nitride, suicides thereof, derivatives thereof, or combinationsthereof. Substrates may have various dimensions, such as 200 mm or 300mm diameter wafers, as well as, rectangular or square panes. Unlessotherwise noted, embodiments and examples described herein arepreferably conducted on substrates with a 200 mm diameter or a 300 mmdiameter, more preferably, a 300 mm diameter. Processes of someembodiments described herein may be utilized to deposit titanium nitrideand other titanium materials (e.g., metallic titanium or titaniumsilicon nitride) on many substrates and surfaces. Substrates on whichembodiments of the invention may be useful include, but are not limitedto semiconductor wafers, such as crystalline silicon (e.g., Si<100> orSi<111>), silicon oxide, strained silicon, silicon germanium, doped orundoped polysilicon, doped or undoped silicon wafers and patterned ornon-patterned wafers. Substrates may be exposed to a pretreatmentprocess to polish, etch, reduce, oxidize, hydroxylate, anneal and/orbake the substrate surface.

“Atomic layer deposition” (ALD) or “cyclical deposition” as used hereinrefers to the sequential introduction of two or more reactive compoundsto deposit a layer of material on a substrate surface. The two, three ormore reactive compounds may alternatively be introduced into a reactionzone or process region of a deposition chamber. The reactive compoundsmay be in a state of gas, plasma, vapor, fluid or other state of matteruseful for a vapor deposition process. Usually, each reactive compoundis separated by a time delay to allow each compound to adhere and/orreact on the substrate surface. In one aspect, a first precursor orcompound A is pulsed into the reaction zone followed by a first timedelay. Next, a second precursor or compound B is pulsed into thereaction zone followed by a second delay. Compound A and compound Breact to form a deposited material. During each time delay a purge gasis introduced into the deposition chamber to purge the reaction zone orotherwise remove any residual reactive compound or by-products from thereaction zone. Alternatively, the purge gas may flow continuouslythroughout the deposition process so that only the purge gas flowsduring the time delay between pulses of reactive compounds. The reactivecompounds are alternatively pulsed until a desired film thickness of thedeposited material is formed on the substrate surface. In eitherscenario, the ALD process of pulsing compound A, purge gas, pulsingcompound B and purge gas is a cycle. A cycle can start with eithercompound A or compound B and continue the respective order of the cycleuntil achieving a film with the desired thickness. In anotherembodiment, a first precursor containing compound A, a second precursorcontaining compound B and a third precursor containing compound C areeach separately pulsed into the deposition chamber. Alternatively, apulse of a first precursor may overlap in time with a pulse of a secondprecursor while a pulse of a third precursor does not overlap in timewith either pulse of the first and second precursors.

“Process gas” as used herein refers to a single gas, multiple gases, agas containing a plasma, combinations of gases and/or plasmas. A processgas may contain at least one reactive compound for a vapor depositionprocess. The reactive compounds or reagents may be in a state of gas,plasma, vapor, or fluid during the vapor deposition process. Also, aprocess may contain a purge gas or a carrier gas and not contain areactive compound.

Other ALD Processes

Embodiments of the invention provide methods for depositing a variety ofmetal-containing materials (e.g., tantalum or tungsten containingmaterials) on a substrate by a thermal ALD process or a PE-ALD processby utilizing the PE-ALD chambers and processes described herein. In oneexample, tantalum nitride is deposited by sequentially exposing asubstrate to a tantalum precursor and a plasma during a PE-ALD process.In another example, tungsten nitride is deposited by sequentiallyexposing a substrate to a tungsten precursor and a plasma during aPE-ALD process. In other examples, metallic tantalum or metallictungsten is deposited by sequentially exposing a substrate to a tantalumprecursor or a tungsten precursor and a plasma during a PE-ALD process.

Tantalum precursors useful during vapor deposition processes asdescribed herein include pentakis(dimethylamido)tantalum (PDMAT orTa(NMe₂)₅), pentakis(ethylmethylamido)tantalum (PEMAT or Ta[N(Et)Me]₅),pentakis(diethylamido)tantalum (PDEAT or Ta(NEt₂)₅,),ethylimido-tris(dimethylamido) tantalum ((EtN)Ta(NMe₂)₃),ethylimido-tris(diethylamido)tantalum ((EtN)Ta(NEt₂)₃),ethylimido-tris(ethylmethylamido)tantalum ((EtN)Ta[N(Et)Me]₃),tertiarybutylimido-tris(dimethylamido)tantalum (TBTDMT or(^(t)BuN)Ta(NMe₂)₃), tertiarybutylimido-tris(diethylamido)tantalum(TBTDET or (^(t)BuN)Ta(NEt₂)₃),tertiarybutylimido-tris(ethylmethylamido)tantalum (TBTEAT or(^(t)BuN)Ta[N(Et)Me]₃), tertiaryamylimido-tris(dimethylamido)tantalum(TAIMATA or (^(t)AmylN)Ta(NMe₂)₃, wherein tamyl is the tertiaryamylgroup (C₅H₁,- or CH₃CH₂C(CH₃)₂—),tertiaryamylimido-tris(diethylamido)tantalum (TAIEATA or (^(t)AmylN)Ta(NEt₂)₃, tertiaryamylimido-tris(ethylmethylamido)tantalum (TAI MATA or(^(t)AmylN)Ta([N(Et)Me]₃), tantalum halides (e.g., TaF₅ or TaCl₅),derivatives thereof, or combinations thereof.

Tungsten precursors that may be useful during the vapor depositionprocesses as described herein include bis(tertiarybutylimido)bis(tertiarybutylamido)tungsten ((^(t)BuN)₂W(N(H)^(t)Bu)₂),bis(tertiarybutylimido) bis(dimethylamido)tungsten ((^(t)BuN)₂W(NMe₂)₂),bis(tertiarybutylimido) bis(diethylamido)tungsten ((^(t)BuN)₂W(NEt₂)₂),bis(tertiarybutylimido) bis(ethylmethylamido)tungsten((^(t)BuN)₂W(NEtMe)₂), tungsten hexafluoride, derivatives thereof, orcombinations thereof.

Nitrogen precursors that may be useful for forming a metal-containingmaterial during the vapor deposition processes as described hereininclude nitrogen (e.g., plasma, N₂, or atomic-N), ammonia (NH₃),hydrazine (N₂H₄), methylhydrazine (Me(H)NNH₂), dimethyl hydrazine(Me₂NNH₂ or Me(H)NN(H)Me), tertiarybutylhydrazine (^(t)Bu(H)NNH₂),phenylhydrazine (C₆H₅(H)NNH₂), a nitrogen plasma source (e.g., N, N₂,N₂/H₂, NH₃, or a N₂H₄ plasma), 2,2′-azotertbutane (^(t)BuNN^(t)Bu), anazide source, such as ethyl azide (EtN₃), trimethylsilyl azide(Me₃SiN₃), derivatives thereof, plasmas thereof, or combinationsthereof.

A suitable reagent for forming a metal-containing material may be areducing gas and include hydrogen (e.g., H₂ or atomic-H), atomic-N,ammonia (NH₃), hydrazine (N₂H₄), silane (SiH₄), disilane (Si₂H₆),trisilane (Si₃H₈), tetrasilane (Si₄H₁₀), dimethylsilane (SiC₂H₈), methylsilane (SiCH₆), ethylsilane (SiC₂H₈), chlorosilane (ClSiH₃),dichlorosilane (Cl₂SiH₂), hexachlorodisilane (Si₂Cl₆), borane (BH₃),diborane (B₂H₆), triborane, tetraborane, pentaborane, triethylborane(Et₃B), derivatives thereof, plasmas thereof, or combinations thereof.

A carrier gas, a purge gas and a process gas may contain nitrogen,hydrogen, ammonia, argon, neon, helium, or combinations thereof. Aplasma may be ignited containing any of these gases. Preferably, aplasma precursor gas that may be useful for forming a metal-containingmaterial during the vapor deposition processes as described hereininclude nitrogen, hydrogen, ammonia, argon or combinations thereof. Inone example, a plasma contains nitrogen and hydrogen. In anotherexample, a plasma contains nitrogen and ammonia. In another example, aplasma contains ammonia and hydrogen.

Metal-containing materials that may be formed during thermal ALD orPE-ALD processes as described herein include tantalum, tantalum nitride,tungsten, tungsten nitride, titanium, titanium nitride, alloys thereof,derivatives thereof or combinations thereof. In one embodiment, ametal-containing material may be formed during a PE-ALD processcontaining a constant flow of a reagent gas while providing sequentialpulses of a metal precursor and a plasma. In another embodiment, ametal-containing material may be formed during another PE-ALD processthat provides sequential pulses of a metal precursor and a reagentplasma. In both of these embodiments, the reagent is generally ionizedduring the process. Embodiments provide that the plasma may be generatedexternal from the deposition chamber, such as by a remote plasmagenerator (RPS) system. During PE-ALD processes, a plasma may begenerated from a microwave (MW) frequency generator or a radio frequency(RF) generator. The plasma may be ignited within the RPS system anddelivered into deposition chamber. In many embodiments, the plasma maybe delivered through the central channel of the inlet manifold assembly,through the showerhead assembly, and into deposition chamber.

The RF generator may be set at a frequency within a range from about 100KHz to about 1.6 MHz. In one example, a RF generator, with a frequencyof 13.56 MHz, may be set to have a power output within a range fromabout 100 watts to about 1,000 watts, preferably, from about 250 wattsto about 600 watts, and more preferably, from about 300 watts to about500 watts. In one example, a RF generator, with a frequency of 400 KHz,may be set to have a power output within a range from about 200 watts toabout 2,000 watts, preferably, from about 500 watts to about 1,500watts. A surface of substrate may be exposed to a plasma having a powerper surface area value within a range from about 0.01 watts/cm² to about10.0 watts/cm², preferably, from about 0.05 watts/cm² to about 6.0watts/cm².

The ALD process provides that the deposition chamber may be pressurizedat a pressure within a range from about 0.1 Torr to about 80 Torr,preferably from about 0.5 Torr to about 10 Torr, and more preferably,from about 1 to about 5. Also, the chamber or the substrate may beheated to a temperature of less than about 500° C., preferably within arange from about 100° C. to about 450° C., and more preferably, fromabout 150° C. to about 400° C., for example, about 300° C. In anotherembodiment, a metal-containing material may be formed during a thermalALD process that provides sequential pulses of a metal precursor and areagent.

The substrate may be for example, a silicon substrate having aninterconnect pattern defined in one or more dielectric material layersformed thereon. In example, the substrate contains a barrier layerthereon, while in another example, the substrate contains a dielectricsurface. The deposition chamber conditions such as, the temperature andpressure, are adjusted to enhance the adsorption of the process gases onthe substrate so as to facilitate the reaction of the pyrrolyl metalprecursors and the reagent gas.

In one embodiment, the substrate may be exposed to a reagent gasthroughout the whole ALD cycle. The substrate may be exposed to a metalprecursor gas formed by passing a carrier gas (e.g., nitrogen or argon)through an ampoule of a metal precursor. The ampoule may be heateddepending on the metal precursor used during the process. The metalprecursor gas usually has a flow rate within a range from about 100 sccmto about 2,000 sccm, preferably, from about 200 sccm to about 1,000sccm, and more preferably, from about 300 sccm to about 700 sccm, forexample, about 500 sccm. The metal precursor gas and the reagent gas maybe combined to form a deposition gas. A reagent gas usually has a flowrate within a range from about 100 sccm to about 3,000 sccm, preferably,from about 200 sccm to about 2,000 sccm, and more preferably, from about500 sccm to about 1,500 sccm. In one example, ammonia is used as areagent gas with a flow rate of about 1,500 sccm. The substrate may beexposed to the metal precursor gas or the deposition gas containing themetal precursor and the reagent gas for a time period within a rangefrom about 0.1 seconds to about 8 seconds, preferably, from about 1second to about 5 seconds, and more preferably, from about 2 seconds toabout 4 seconds. The flow of the metal precursor gas may be stopped oncethe metal precursor is adsorbed on the substrate. The metal precursormay be a discontinuous layer, continuous layer or even multiple layers.

The substrate and deposition chamber may be exposed to a purge stepafter stopping the flow of the metal precursor gas. The flow rate of thereagent gas may be maintained or adjusted from the previous step duringthe purge step. Preferably, the flow of the reagent gas is maintainedfrom the previous step. Optionally, a purge gas may be administered intothe deposition chamber with a flow rate within a range from about 100sccm to about 2,000 sccm, preferably, from about 200 sccm to about 1,000sccm, and more preferably, from about 300 sccm to about 700 sccm, forexample, about 500 sccm. The purge step removes any excess metalprecursor and other contaminants within the deposition chamber. Thepurge step may be conducted for a time period within a range from about0.1 seconds to about 8 seconds, preferably, from about 1 second to about5 seconds, and more preferably, from about 2 seconds to about 4 seconds.The carrier gas, the purge gas and the process gas may contain nitrogen,hydrogen, ammonia, argon, neon, helium, or combinations thereof. In apreferred embodiment, the carrier gas contains nitrogen.

Thereafter, the flow of the reagent gas may be maintained or adjustedbefore igniting a plasma. The substrate may be exposed to the plasma fora time period within a range from about 0.1 seconds to about 20 seconds,preferably, from about 1 second to about 10 seconds, and morepreferably, from about 2 seconds to about 8 seconds. Thereafter, theplasma power was turned off. In one example, the reagent may be ammonia,nitrogen, hydrogen or a combination thereof to form an ammonia plasma, anitrogen plasma, a hydrogen plasma or a combined plasma. The reactantplasma reacts with the adsorbed metal precursor on the substrate to forma metal-containing material thereon. In one example, the reactant plasmais used as a reducing agent to form metallic ruthenium, tantalum,tungsten, titanium, or alloys thereof. However, a variety of reactantsmay be used to form metal-containing materials having a wide range ofcompositions. In one example, a boron-containing reducing compound(e.g., diborane) is used to form a metal-containing material containingboride. In another example, a silicon-containing reducing compound(e.g., silane) is used to form a metal-containing material containingsilicide.

The deposition chamber was exposed to a second purge step to removeexcess precursors or contaminants from the previous step. The flow rateof the reagent gas may be maintained or adjusted from the previous stepduring the purge step. An optional purge gas may be administered intothe deposition chamber with a flow rate within a range from about 100sccm to about 2,000 sccm, preferably, from about 200 sccm to about 1,000sccm, and more preferably, from about 300 sccm to about 700 sccm, forexample, about 500 sccm. The second purge step may be conducted for atime period within a range from about 0.1 seconds to about 8 seconds,preferably, from about 1 second to about 5 seconds, and more preferably,from about 2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of themetal-containing material is deposited on the substrate. Themetal-containing material may be deposited with a thickness less than1,000 Å, preferably less than 500 Å and more preferably from about 10 Åto about 100 Å, for example, about 30 Å. The processes as describedherein may deposit a metal-containing material at a rate of at least0.15 Å/cycle, preferably, at least 0.25 Å/cycle, more preferably, atleast 0.35 Å/cycle or faster. In another embodiment, the processes asdescribed herein overcome shortcomings of the prior art relative asrelated to nucleation delay. There is no detectable nucleation delayduring many, if not most, of the experiments to deposit themetal-containing materials.

In another embodiment, a metal-containing material may be formed duringanother PE-ALD process that provides sequentially exposing the substrateto pulses of a metal precursor and an active reagent, such as a reagentplasma. The substrate may be exposed to a metal precursor gas formed bypassing a carrier gas through an ampoule containing a metal precursor,as described herein. The metal precursor gas usually has a flow ratewithin a range from about 100 sccm to about 2,000 sccm, preferably, fromabout 200 sccm to about 1,000 sccm, and more preferably, from about 300sccm to about 700 sccm, for example, about 500 sccm. The substrate maybe exposed to the deposition gas containing the metal precursor and thereagent gas for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably from about 2 seconds to about 4 seconds. The flow of themetal precursor gas may be stopped once the metal precursor is adsorbedon the substrate. The metal precursor may be a discontinuous layer,continuous layer or even multiple layers.

Subsequently, the substrate and chamber are exposed to a purge step. Apurge gas may be administered into the deposition chamber during thepurge step. In one aspect, the purge gas is the reagent gas, such asammonia, nitrogen or hydrogen. In another aspect, the purge gas may be adifferent gas than the reagent gas. For example, the reagent gas may beammonia and the purge gas may be nitrogen, hydrogen or argon. The purgegas may have a flow rate within a range from about 100 sccm to about2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm, andmore preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The purge step removes any excess metal precursor andother contaminants within the deposition chamber. The purge step may beconducted for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably, from about 2 seconds to about 4 seconds. A carrier gas,a purge gas, and/or a process gas may contain nitrogen, hydrogen,ammonia, argon, neon, helium, plasmas thereof, or mixtures thereof.

The substrate and the adsorbed metal precursor thereon may be exposed tothe reagent gas during the next step of the ALD process. Optionally, acarrier gas may be administered at the same time as the reagent gas intothe deposition chamber. The reagent gas may be ignited by the RPS toform a plasma. The reagent gas usually has a flow rate within a rangefrom about 100 sccm to about 3,000 sccm, preferably, from about 200 sccmto about 2,000 sccm, and more preferably, from about 500 sccm to about1,500 sccm. In one example, ammonia is used as a reagent gas with a flowrate of about 1,500 sccm. The substrate may be exposed to the plasma fora time period within a range from about 0.1 seconds to about 20 seconds,preferably, from about 1 second to about 10 seconds, and morepreferably, from about 2 seconds to about 8 seconds. Thereafter, theplasma power may be turned off. In one example, the reagent may beammonia, nitrogen, hydrogen or combinations thereof, while the plasmamay be an ammonia plasma, a nitrogen plasma, a hydrogen plasma or acombination thereof. The reactant plasma reacts with the adsorbed metalprecursor on the substrate to form a metal-containing material thereon.Preferably, the reactant plasma is used as a reducing agent or as anitrogen source to form metal layers or nitride layers of ruthenium,tantalum, tungsten, titanium or alloys thereof. However, a variety ofreactants may be used to form metal-containing materials having a widerange of compositions, as described herein.

The deposition chamber may be exposed to a second purge step to removeexcess precursors or contaminants from the deposition chamber. The flowof the reagent gas may have been stopped at the end of the previous stepand started during the purge step, if the reagent gas is used as a purgegas. Alternative, a purge gas that is different than the reagent gas maybe administered into the deposition chamber. The reagent gas or purgegas may have a flow rate within a range from about 100 sccm to about2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm, andmore preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The second purge step may be conducted for a time periodwithin a range from about 0.1 seconds to about 8 seconds, preferably,from about 1 second to about 5 seconds, and more preferably, from about2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of themetal-containing material is deposited on the substrate. Themetal-containing material may be deposited with a thickness less than1,000 Å, preferably less than 500 Å and more preferably from about 10 Åto about 100 Å, for example, about 30 Å. The processes as describedherein may deposit a metal-containing material at a rate of at least0.15 Å/cycle, preferably, at least 0.25 Å/cycle, more preferably, atleast 0.35 Å/cycle or faster. In another embodiment, the processes asdescribed herein overcome shortcomings of the prior art relative asrelated to nucleation delay. There is no detectable nucleation delayduring many, if not most, of the experiments to deposit themetal-containing materials.

The time interval for the pulse of the metal precursor is variabledepending upon a number of factors such as, for example, the volumecapacity of the deposition chamber employed, the vacuum system coupledthereto and the volatility/reactivity of the reactants used during theALD process. For example, (1) a large-volume deposition chamber may leadto a longer time to stabilize the process conditions such as, forexample, carrier/purge gas flow and temperature, requiring a longerpulse time; (2) a lower flow rate for the process gas may also lead to alonger time to stabilize the process conditions requiring a longer pulsetime; and (3) a lower chamber pressure means that the process gas isevacuated from the deposition chamber more quickly requiring a longerpulse time. In general, the process conditions are advantageouslyselected so that a pulse of the metal precursor provides a sufficientamount of precursor so that at least a monolayer of the metal precursoris adsorbed on the substrate. Thereafter, excess metal precursorremaining in the chamber may be removed from the deposition chamber bythe constant carrier gas stream in combination with the vacuum system.

The time interval for each of the pulses of the metal precursor and thereagent gas may have the same duration. That is, the duration of thepulse of the metal precursor may be identical to the duration of thepulse of the reagent gas. For such an embodiment, a time interval (T₁)for the pulse of the metal precursor is equal to a time interval (T₂)for the pulse of the reagent gas.

Alternatively, the time interval for each of the pulses of the metalprecursor and the reagent gas may have different durations. That is, theduration of the pulse of the metal precursor may be shorter or longerthan the duration of the pulse of the reagent gas. For such anembodiment, a time interval (T₁) for the pulse of the metal precursor isdifferent than the time interval (T₂) for the pulse of the reagent gas.

In addition, the periods of non-pulsing between each of the pulses ofthe metal precursor and the reagent gas may have the same duration. Thatis, the duration of the period of non-pulsing between each pulse of themetal precursor and each pulse of the reagent gas is identical. For suchan embodiment, a time interval (T₃) of non-pulsing between the pulse ofthe metal precursor and the pulse of the reagent gas is equal to a timeinterval (T₄) of non-pulsing between the pulse of the reagent gas andthe pulse of the metal precursor. During the time periods of non-pulsingonly the constant carrier gas stream is provided to the depositionchamber.

Alternatively, the periods of non-pulsing between each of the pulses ofthe metal precursor and the reagent gas may have different duration.That is, the duration of the period of non-pulsing between each pulse ofthe metal precursor and each pulse of the reagent gas may be shorter orlonger than the duration of the period of non-pulsing between each pulseof the reagent gas and the metal precursor. For such an embodiment, atime interval (T₃) of non-pulsing between the pulse of the metalprecursor and the pulse of the reagent gas is different from a timeinterval (T₄) of non-pulsing between the pulse of the reagent gas andthe pulse of metal precursor. During the time periods of non-pulsingonly the constant carrier gas stream is provided to the depositionchamber.

Additionally, the time intervals for each pulse of the metal precursor,the reagent gas and the periods of non-pulsing therebetween for eachdeposition cycle may have the same duration. For such an embodiment, atime interval (T₁) for the metal precursor, a time interval (T₂) for thereagent gas, a time interval (T₃) of non-pulsing between the pulse ofthe metal precursor and the pulse of the reagent gas and a time interval(T₄) of non-pulsing between the pulse of the reagent gas and the pulseof the metal precursor each have the same value for each depositioncycle. For example, in a first deposition cycle (C₁), a time interval(T₁) for the pulse of the metal precursor has the same duration as thetime interval (T₁) for the pulse of the metal precursor in subsequentdeposition cycles (C₂. . . C_(n)). Similarly, the duration of each pulseof the reagent gas and the periods of non-pulsing between the pulse ofthe metal precursor and the reagent gas in the first deposition cycle(C₁) is the same as the duration of each pulse of the reagent gas andthe periods of non-pulsing between the pulse of the metal precursor andthe reagent gas in subsequent deposition cycles (C₂ . . . C_(n)),respectively.

Alternatively, the time intervals for at least one pulse of the metalprecursor, the reagent gas and the periods of non-pulsing therebetweenfor one or more of the deposition cycles of the metal-containingmaterial deposition process may have different durations. For such anembodiment, one or more of the time intervals (T₁) for the pulses of themetal precursor, the time intervals (T₂) for the pulses of the reagentgas, the time intervals (T₃) of non-pulsing between the pulse of themetal precursor and the reagent gas and the time intervals (T₄) ofnon-pulsing between the pulses of the reagent gas and the metalprecursor may have different values for one or more deposition cycles ofthe cyclical deposition process. For example, in a first depositioncycle (C₁), the time interval (T₁) for the pulse of the metal precursormay be longer or shorter than one or more time interval (T₁) for thepulse of the metal precursor in subsequent deposition cycles (C₂. . .C_(n)). Similarly, the durations of the pulses of the reagent gas andthe periods of non-pulsing between the pulse of the metal precursor andthe reagent gas in the first deposition cycle (C₁) may be the same ordifferent than the duration of each pulse of the reagent gas and theperiods of non-pulsing between the pulse of the metal precursor and thereagent gas in subsequent deposition cycles (C₂ . . . C_(n)).

In some embodiments, a constant flow of a carrier gas or a purge gas maybe provided to the deposition chamber modulated by alternating periodsof pulsing and non-pulsing where the periods of pulsing alternatebetween the metal precursor and the reagent gas along with thecarrier/purge gas stream, while the periods of non-pulsing include onlythe carrier/purge gas stream.

While foregoing is directed to the preferred embodiment of theinvention, other and further embodiments of the invention may be devisedwithout departing from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. A chamber for plasma-enhanced atomic layer deposition processes,comprising: a substrate support containing a substrate receiving surfaceand disposed within a chamber body; a chamber lid assembly coupled withthe chamber body and comprising: an inlet manifold assembly comprisingan annular channel encompassing a centralized channel, wherein thecentralized channel extends through the inlet manifold assembly, theinlet manifold assembly further comprises injection holes extending fromthe annular channel, through a sidewall of the centralized channel, andto the centralized channel; a showerhead assembly comprising ashowerhead plate disposed below the inlet manifold assembly; a water boxdisposed between the inlet manifold assembly and the showerheadassembly; and a remote plasma system disposed above and coupled with theinlet manifold assembly, and in fluid communication with the centralizedchannel; and a processing region disposed between the substratereceiving surface and a lower surface of the showerhead plate.
 2. Thechamber of claim 1, wherein the injection holes comprise a firstplurality of injection holes extending towards or substantially towardsa central axis of the centralized channel.
 3. The chamber of claim 2,wherein the first plurality of injection holes contains three or moreinjection holes.
 4. The chamber of claim 2, wherein the injection holescomprise a second plurality of injection holes extending tangential orsubstantially tangential towards the sidewall of the centralizedchannel.
 5. The chamber of claim 4, wherein the second plurality ofinjection holes are disposed along the sidewall of the centralizedchannel and between the first plurality of injection holes and theshowerhead assembly.
 6. The chamber of claim 2, wherein the injectionholes comprise a second plurality of injection holes extending at adifferent angle than the first plurality of holes.
 7. The chamber ofclaim 6, wherein the first plurality of injection holes contains threeor more injection holes and the second plurality of injection holescontains three or more injection holes.
 8. The chamber of claim 1,wherein each injection hole has a diameter within a range from about0.06 inches to about 0.12 inches.
 9. The chamber of claim 1, wherein theinlet manifold assembly comprises aluminum or an aluminum alloy.
 10. Thechamber of claim 9, wherein the inlet manifold assembly comprises analuminum alloy, and the aluminum alloy further comprises magnesium andsilicon.
 11. The chamber of claim 1, further comprising a gas manifoldassembly coupled with and in fluid communication with the inlet manifoldassembly.
 12. The chamber of claim 11, wherein the gas manifold assemblycomprises a first conduit coupled with and in fluid communication withthe annular channel.
 13. The chamber of claim 12, wherein a valveassembly is coupled with and in fluid communication with the firstconduit, and the valve assembly comprises a mass flow controller toenable an atomic layer deposition process.
 14. The chamber of claim 12,wherein the gas manifold assembly comprises a second conduit coupledwith and in fluid communication with the annular channel.
 15. Thechamber of claim 12, wherein the gas manifold assembly comprises asecond conduit coupled with and in fluid communication with the remoteplasma system.
 16. The chamber of claim 1, wherein the remote plasmasystem is disposed at the upper end of the centralized channel and theshowerhead assembly is disposed at the lower end of the centralizedchannel.
 17. A method for depositing a material on a substrate,comprising: exposing a substrate sequentially to a titanium precursorgas and a nitrogen plasma to form a titanium nitride material on thesubstrate during an atomic layer deposition process within a depositionchamber, wherein the titanium precursor gas comprisestetrakis(dimethylamido)titanium, the nitrogen plasma is generated from aremote plasma system, and the atomic layer deposition process comprises:flowing the titanium precursor gas into an annular channel within aninlet manifold assembly, wherein the annular channel encompasses acentralized channel, the centralized channel extends through the inletmanifold assembly, and a chamber lid assembly comprising the inletmanifold assembly is coupled with a chamber body forming the depositionchamber; flowing the titanium precursor gas from the annular channelinto the centralized channel via a plurality of injection holes whichextend from the annular channel through a sidewall of the centralizedchannel, and to the centralized channel; flowing the titanium precursorgas through the centralized channel, through a showerhead assemblyattached with the chamber lid assembly, and absorbing a layer of thetetrakis(dimethylamido)titanium on the substrate; generating thenitrogen plasma by igniting a process gas comprising nitrogen (N₂) withthe remote plasma system; flowing the nitrogen plasma through thecentralized channel, through the showerhead assembly, and towards thesubstrate; and exposing the layer of the tetrakis(dimethylamido)titaniumto the nitrogen plasma to form the titanium nitride material on thesubstrate.
 18. The method of claim 17, wherein the injection holescomprise a first plurality of injection holes extending towards orsubstantially towards a central axis of the centralized channel.
 19. Themethod of claim 18, wherein the injection holes comprise a secondplurality of injection holes extending tangential or substantiallytangential towards the sidewall of the centralized channel.
 20. Themethod of claim 19, wherein the first plurality of injection holescontains three or more injection holes and the second plurality ofinjection holes contains three or more injection holes.
 21. The methodof claim 19, further comprising flowing the titanium precursor gasthrough the second plurality of injection holes to form a circular gasflow of the titanium precursor gas through the centralized channel. 22.The method of claim 21, wherein the circular gas flow has a flow patternselected from the group consisting of a vortex flow pattern, a helixflow pattern, a spiral flow pattern, a swirl flow pattern, a twirl flowpattern, a twist flow pattern, a coil flow pattern, a corkscrew flowpattern, a curl flow pattern, a whirlpool flow pattern, and a derivativethereof.
 23. A showerhead assembly for a vapor deposition process,comprising: a showerhead plate comprising a top surface, a bottomsurface, and a radius extending from the center to the outer edge of theshowerhead plate; a first plurality of holes in fluid communication withthe top surface and the bottom surface, positioned within a first zoneextending from the center of the showerhead plate to about 25% of theradius of the showerhead plate, and each hole comprises a diameter ofless than 0.1 inches; and a second plurality of holes in fluidcommunication with the top surface and the bottom surface, positionedwithin a second zone extending from about 25% of the radius of theshowerhead plate to about the outer edge of the showerhead plate, andeach hole comprises a diameter of greater than 0.1 inches.
 24. Theshowerhead assembly of claim 23, wherein the showerhead plate comprisesan increasing hole density radially extending towards the outer edge.25. The showerhead assembly of claim 23, wherein the showerhead platecomprises an aluminum alloy, and the aluminum alloy further comprisesmagnesium and silicon.